CN101302296B - Preparation of amphiphilic copolymer self-assembled micelle wedding agent - Google Patents
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Abstract
一种双亲性共聚物自组装胶束乳化剂的制备方法，属于高分子材料技术领域。双亲性共聚物由亲水单体和疏水单体共聚，或几种不同类型的亲水单体共聚、或几种不同类型的疏水单体共聚得到；再在选择性溶剂中，进行双亲性共聚物溶液自组装，得到双亲性共聚物胶束；该共聚物组装胶束可以稳定的分散在油水界面上，隔离油水相形成十分稳定的乳化分散体系。共聚物组装胶束粒径在微纳米范畴内，可以单独作为乳化剂或与其它乳化剂复配使用。
The invention discloses a preparation method of an amphiphilic copolymer self-assembled micelle emulsifier, which belongs to the technical field of polymer materials. Amphiphilic copolymers are obtained by copolymerization of hydrophilic monomers and hydrophobic monomers, or copolymerization of several different types of hydrophilic monomers, or copolymerization of several different types of hydrophobic monomers; then amphiphilic copolymerization is carried out in a selective solvent The amphiphilic copolymer micelle is obtained by self-assembly of the substance solution; the copolymer assembled micelle can be stably dispersed on the oil-water interface, and the oil-water phase is separated to form a very stable emulsified dispersion system. The particle size of the copolymer assembled micelles is in the range of micronano and can be used alone as an emulsifier or in combination with other emulsifiers.
Description
Technical field
The present invention relates to a kind of preparation method of amphiphilic copolymer self-assembled micelle wedding agent, by the synthetic polymer of molecular designing with specific functionality, obtain having the micella of environment-responsive by self-assembly, can be used as emulsifying agent, belong to technical field of polymer materials.
Background technology
Emulsifying agent has a wide range of applications in fields such as food, pharmacy, makeup, coating, the energy.Yet mostly existing emulsifying agent is the small molecules tensio-active agent, because its unstable and transportable characteristics make it exist critical defect in the food safety and sanitation field.In recent years, along with the develop rapidly of nanotechnology, the particle emulsifying agent embodies its excellent performance gradually, has attracted more and more investigators' sight.
As far back as 20 beginnings of the century, Pickering just recognizes that the micro-solid particle can be used as emulsifying agent, and he uses copper sulfate, ferric sulfate stable emulsifying water and paraffin system.Early 1980s, the solid particulate emulsifying agent begins to be applied in the skin care product prescription, is mainly used in the antianaphylaxis prescription and sunscreen product prescription of no chemical emulsifier.In recent years, people such as B.P.Binks to the research of environment-responsive particle emulsifying agent, have promoted the tremendous development that such emulsifying agent is theoretical and use to the research of solid particulate emulsifying agent emulsification mechanism and people such as S.Fujii, S.P.Armes.
Because the solid particulate emulsifying agent generally will obtain nano-scale particle earlier, applied research comprise inorganic solid particles, polymer solid particles and solid lipid particle, then particle is being carried out surface modification, to obtain the suitable emulsifying agent of series.But previous step just relates to problems, as the dispersion of nano particle, stable or the like, simultaneously, particularly importantly, to the functionalization of particle surface---make the particle emulsifying agent have very difficulty of environment-responsive.Yet, if adopt the self-assembling technique of amphiphilic polymkeric substance, just can fundamentally simplify the preparation process of particle emulsifying agent, but also can be from self assembling process, accurately the micella particle grain size that finally obtains of control with and surface property, simultaneously, can obtain finally to have the micelle wedding agent of specific function from the angle of molecular designing.
So-called self-assembly is meant amphiphilic polymer molecule under weak interaction forces such as hydrogen bond, electrostatic interaction, Van der Waals force promote, the spontaneous process that is built into the aggregate with special construction and shape.Polymkeric substance of the present invention be simple and easy to, amphiphilic random copolymers or alternating copolymer that can suitability for industrialized production, can obtain amphiphilic, particle diameter in surface and the adjustable micella of form by assembling, by the light dimerization reaction of photosensitive group, can examine (or shell) thus the crosslinked emulsifying agent that obtains stable performance; Simultaneously, can also be by design to molecular structure, the amphiphilic particle that obtains having specific functionality after self-assembly is such as pH value susceptibility, temperature sensitive property, ionogen susceptibility and sensitivity of light.Therefore, can change the particle surface contact angle by environmental stimulus, particle form etc. reach the purpose of control emulsion, thereby increase the potential range of application of this function emulsifying agent.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of amphiphilic copolymer self-assembled micelle wedding agent, at deficiency in the existing particle emulsifying agent preparation and functionalization easily, a kind of method easy, that can accurately control again is provided, promptly prepares amphiphilic micelle wedding agent by self-assembling technique with amphiphilic copolymer.
Another object of the present invention also is to control micelle wedding agent from molecular designing angle and self assembling process, and it can have characteristics such as specific functionality and environmental stimulus responsiveness.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of amphiphilic copolymer self-assembled micelle wedding agent, and its technology is:
(1) preparation amphiphilic copolymer: amphiphilic copolymer is by hydrophilic monomer and hydrophobic monomer copolymerization, or several dissimilar hydrophilic monomer copolymerization or several dissimilar hydrophobic monomer copolymerization obtain;
Used hydrophilic monomer is selected from:
(a) maleic anhydride, (methyl) vinylformic acid, to vinyl benzoic acid;
(b) 4-vinylpridine, 2-vinyl pyridine, (methyl) vinylformic acid-2-(dimethylamino) ethyl ester, diethylamine ethyl-methyl acrylate;
(c) to vinylbenzenesulfonic acid, (methyl) acryloyl oxyethyl group trimethyl ammonium chloride, (methyl) acrylamide, N, N`-DMAA, N dimethylamine ethyl-methyl acrylamide;
(d) (methyl) vinylformic acid hydroxyl second (third) ester, N-N-isopropylacrylamide etc.;
Used hydrophobic monomer is selected from:
(e) vinylbenzene, (methyl) esters of acrylic acid, vinyl acetate;
(f) (methyl) acryloyl ethoxy-cinnamic acid ester, 4-methyl-7-are to the inferior methoxy coumarin of vinyl benzene;
By the copolymerization process of two or more dissimilar monomer by common free radical solution polymerization, free radical dispersion polymerization, free-radical emulsion polymerization or free radical precipitation polymerization, the preparation amphiphilic copolymer;
(2) carry out the self-assembly of amphiphilic copolymer solution: in selective solvent, carry out the self-assembly of amphiphilic copolymer solution, obtain the amphiphilic copolymer micella; Selective solvent is made up of cosolvent and precipitation agent, wherein cosolvent can dissolve the polymer segment that two kinds of dissimilar monomers are formed simultaneously, selects for use: dimethyl formamide, dimethyl sulfoxide (DMSO), dioxane, tetrahydrofuran (THF), acetone, Virahol, butanols or mixed solvent; Precipitation agent is a kind of segmental good solvent in the multipolymer, is another kind of segmental precipitation agent in the multipolymer, selects for use: water, ethanol or toluene; Be dissolved in amphiphilic copolymer in the cosolvent fully, amphiphilic copolymer solution quality concentration range is 0.5%-30%, stir the precipitation agent that slowly splashes into 0.1-2 times of cosolvent volume down, make multipolymer generation microphase-separated, self-assembly forms stable amphiphilic copolymer assembling micellar solution, dropwise the back at precipitation agent and continue at the uniform velocity to stir 2-12 hour, make the polymer chain assembling fully; The micella median size of being assembled out is between 10～800nm.
(3) micella immobilization: the amphiphilic copolymer of self-assembly assembling micellar solution is dropwise added 2-10 doubly in the precipitation agent of cosolvent volumetric usage, make micella stable; Continue to stir after 1-3 hour and displace cosolvent or adopt volatilization method to steam cosolvent (for example lower boiling tetrahydrofuran (THF), acetone by dialysis method, this method generally is used for the preparation of reversed phase micelle emulsifying agent), obtain amphipathic multipolymer assembling micellar solution, this amphipathic multipolymer assembling micella exists with micella particle solution form, or, use as micelle wedding agent through lyophilize or the spray-dried solid gums bundle of particle that obtains.
Described preparation method, that is adopted is common free-radical polymerized, from the angle Selection of molecular designing dissimilar comonomer and ratio thereof, thereby regulates both sexes segmental ratio in the final resulting polymers segment; The adjusting of both sexes segment ratio in the polymkeric substance, the controllability of decision micelle wedding agent particle performance.
The amphiphilic copolymer of preparation by initial molecular designing, makes multipolymer have the responsive responsiveness of (a) pH; (b) temperature sensitive response; (c) ion-sensitive responsiveness; (d) photaesthesia responsiveness.
Described preparation method carries out the self-assembly of amphiphilic copolymer solution, controls final micella particle surface hydrophilic and hydrophobic, micella particle diameter by control selective solvent ratio, thereby controls the emulsifying property of final micelle wedding agent.
The micella particle of described method preparation has the responsive responsiveness of (a) pH; (b) temperature sensitive response; (c) ion-sensitive responsiveness; (d) photaesthesia responsiveness.
The application of the micella particle of described method preparation is used as micelle wedding agent, and emulsified oiliness composition is 1-1000 with the ratio of micella particle: 1 mixes; Oil or oiliness composition are selected for use: 1: toluene, hexanaphthene, octane, undecyl alcohol; 2: silicone oil, white oil, stearic acid; 3: heavy oil, kerosene, diesel oil; Or 4: oiliness dyestuff, oiliness initiator, oiliness solidifying agent, actives.
Emulsion preparation: get the micelle wedding agent aqueous solution (the micellar mass concentration is 0.1%-20% in the control solution) that makes by the above technical scheme, 0.1-10 the doubly oil of micelle wedding agent aqueous solution volume or oily matter, under 4000-20000 rev/min rotating speed, homogenize, make required emulsion oil-in-water with hollander; Or get the reversed phase micelle solution (toluene is solvent) that makes by technique scheme, 0.1-10 the doubly water of reversed phase micelle emulsifier solution volume or water-soluble substances, under 4000-20000 rev/min rotating speed, homogenize, make required water-in-oil emulsion with hollander.
Beneficial effect of the present invention: the present invention has overcome in the existing particle emulsifying agent preparation and to the deficiency on its functional modification, adopt amphiphilic random copolymers or alternating copolymer (this multipolymer be simple and easy to, can suitability for industrialized production), by the polymkeric substance assembling can obtain that the surface is amphiphilic, particle diameter and the adjustable micella of form; Simultaneously, can also be by design to molecular structure, the amphiphilic particle that obtains having specific functionality after self-assembly is such as pH value susceptibility, temperature sensitive property, ionogen susceptibility and sensitivity of light.Therefore, can change the particle surface contact angle by environmental stimulus, particle form etc. reach the purpose of control emulsion, thereby increase the range of application of this function emulsifying agent.
Description of drawings
The apparent figure of emulsifying effectiveness under Fig. 1 differing temps, wherein a left side: the effect after 25 ℃ of following emulsification; Right: emulsifying effectiveness under 50 ℃ of conditions.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited thereto.
Embodiment 1
(1) preparation of amphiphilic copolymer
By the free radical precipitation polymerization, synthetic amphiphilic copolymer poly-(vinylbenzene-alt-maleic anhydride) with alternating structure.Weighing vinylbenzene 2.08g (0.02mol), maleic anhydride 1.96g (0.02mol), initiator Diisopropyl azodicarboxylate 0.020g (0.00012mol, by the reaction monomers integral molar quantity 0.3%) in 28mL toluene, inflated with nitrogen 20 minutes, 65 ℃ are reacted 12h down, filter toluene, be dissolved in the 15mL dimethyl formamide, in the ether of dimethyl formamide volume, precipitate at 8 times, filter 30 ℃ of vacuum-dryings.Product is dissolved in the dimethyl formamide, and precipitation is filtered drying.Repeat above-mentioned steps three times, obtain purified amphiphilic alternating copolymer.
(2) preparation of amphiphilic copolymer micelle wedding agent
(1) gained multipolymer is dissolved in the solution that is made into mass concentration 2% in the dimethyl formamide, at the uniform velocity stirs progressively slowly dropping and the isopyknic precipitation agent deionized water of dimethyl formamide in polymers soln down; After dropwising, continue at the uniform velocity to stir 4h, make micella stable in the deionized water with 6 times of dimethyl formamide volumes of the slow adding of mixing solutions then; Displace solvent dimethylformamide by dialysis method after continue stirring 2h, control that the micella mass concentration is 0.5% in the final micellar aqueous solution, promptly can be used as micelle wedding agent (or spray-dried method obtains the solid gums bundle of particle).
(3) emulsion preparation
Get the described micelle wedding agent solution of 100mL step (2), and the oil-soluble colourant that are dissolved in toluene of 100mL, homogeneous 2min under 15000 rev/mins speed obtains extremely stable fine emulsion.This water-based emulsion can be used for the color jet-ink printing and dyeing, and its advantage is to pollute to lack, and can directly print and dye by shower nozzle, and the phenomenon that the oiliness dyestuff stops up shower nozzle can not occur.
Embodiment 2
(1) preparation of amphiphilic copolymer, identical with example 1.
(2) preparation of amphiphilic copolymer micelle wedding agent, identical with example 1.
(3) emulsion preparation
Get the described dispersion and emulsion agent solution of 3mL step (2), add sodium-chlor and regulate its concentration in micellar aqueous solution, and get equal-volume toluene, homogeneous 2min under 15000 rev/mins speed, obtain extremely stable fine emulsion, this type of polyelectrolyte can improve emulsifying effectiveness greatly by adding small molecules ionogen (as sodium-chlor).
Embodiment 3
(1) preparation of amphiphilic copolymer
Synthetic poly-(maleic anhydride-co-vinylbenzene-co-(4-methyl-7-is to the inferior methoxy coumarin of vinyl benzene)) with alternating polymerization tendency.Weighing maleic anhydride 2.352g (0.024mol), vinylbenzene 1.56g (0.015mol), 4-methyl-7-is to the inferior methoxy coumarin 1.33g (0.005mol) of vinyl benzene, initiator Diisopropyl azodicarboxylate 0.072g (0.00044 mol, press the monomer integral molar quantity 1.0%) in the 25mL dioxane, inflated with nitrogen 50 minutes, 65 ℃ are reacted 8h down, in the mixed solvent of 8 times of methanol (volume ratio is 1: 1), precipitate, filter 30 ℃ of vacuum-dryings to the dioxane volume.Product is dissolved in the tetrahydrofuran (THF), and precipitation is filtered drying.Repeat above-mentioned steps three times, obtain purified amphiphilic copolymer with alternating structure tendency.
(2) preparation of amphiphilic copolymer micelle wedding agent
The gained multipolymer is dissolved in to be made into mass concentration in the dioxane be 5% solution, at the uniform velocity stirs the precipitation agent deionized water that progressively in polymers soln, slowly drips 0.5 times of dioxane volume down; After dropwising, continue at the uniform velocity to stir 6h, make micella stable in the deionized water with 6 times of dioxane volumes of the slow adding of mixing solutions then; Displace the dioxane solvent by dialysis method after continuing to stir 2h, control that the micella mass concentration is 0.6% in the final micellar aqueous solution, thereby obtain the micellar aqueous solution of this amphiphilic polymkeric substance, resultant micella particle diameter is about 180nm, with the high voltage mercury lamp irradiation 1h of 1kw, micellar surface generation illumination crosslinking reaction makes the micella immobilization.
(3) preparation of emulsion
Get the described micelle wedding agent 0.5L of step (2), diesel oil 0.5L, homogeneous 15min under 10000 rev/mins speed obtains having emulsifying effectiveness and more stable emulsion preferably, can be used as emulsion fuel.
Embodiment 4
(1) preparation of amphiphilic copolymer
Synthesis of amphoteric gathers (vinylformic acid-2-(dimethylamino) ethyl ester-co-methyl methacrylate-co-methylacryoyloxyethyl laurate).Weighing vinylformic acid-2-(dimethylamino) ethyl ester 2.86g (0.02mol), methyl methacrylate 1.0g (0.01mol), methylacryoyloxyethyl laurate 2.46g (0.01mol), initiator Diisopropyl azodicarboxylate 0.099g (0.0006 mol, press the monomer integral molar quantity 1.5%) in the 25mL dioxane, inflated with nitrogen 20min, 70 ℃ are reacted 12h down, in the mixed solvent of 8 times of methanol (volume ratio is 1: 1), precipitate, filter 30 ℃ of vacuum-dryings to the dioxane volume.Product is dissolved in the tetrahydrofuran (THF), and precipitation is filtered drying.Repeat above-mentioned steps three times, obtain purified amphiphilic copolymer.
(2) preparation of amphiphilic copolymer micelle wedding agent
The multipolymer of gained is dissolved in the solution that is made into mass concentration 2% in the dioxane, at the uniform velocity stirs and progressively in polymers soln, slowly drip 1.5 times down to the precipitation agent deionized water of dioxane volume; Dropwise the back and continue at the uniform velocity to stir 6h, make micella stable in the deionized water with 6 times of dioxane volumes of the slow adding of mixing solutions then; Displace the dioxane solvent by dialysis method after continuing to stir 2h, spray-dried method obtains the solid gums bundle of particle, can cooperate other composition to use as emulsifying agent.
(3) preparation of emulsion
Get above-mentioned solid gums bundle of particle 2g, tween-80 0.5g, white oil 15g and water 15g, homogeneous 5min under 5000 rev/mins speed obtains extremely stable emulsion.Described solid gums bundle of particle and tensio-active agent tween-80 are composite, the stabilized emulsion system that can be used for the makeup type, simultaneously, this material contains the reversible group of ultraviolet light cross-linking, make it have the ultraviolet ability of multiple absorption again, can be used for the occasion of anti-ultraviolet radiation.
Embodiment 5
(1) preparation of amphiphilic copolymer
Synthesis of amphoteric multipolymer poly-(4-vinylpridine-co-vinylformic acid-co-(4-methyl-7-is to the inferior methoxy coumarin of vinyl benzene)).Weighing 0.525g (0.005mol) 4-vinylpridine, 0.36g (0.005mol) vinylformic acid, 2.66g (0.01mol) 4-methyl-7-is to the inferior methoxy coumarin of vinyl benzene, 0.049g the initiator Diisopropyl azodicarboxylate (0.0003mol, press the monomer integral molar quantity 1.5%) in the 25mL dioxane, inflated with nitrogen 20 minutes, 70 ℃ are reacted 12h down, in the mixed solvent of 8 times of methanol (volume ratio is 8: 2), precipitate, filter 30 ℃ of vacuum-dryings to the dioxane volume.Product is dissolved among the THF, and precipitation is filtered drying.Repeat above-mentioned steps three times, obtain the poly-weak electrolyte amphiphilic copolymer of purified both sexes.
(2) preparation of amphiphilic copolymer micelle wedding agent
The amphiphilic copolymer of gained is configured to the solution of mass concentration 3% in dioxane, at the uniform velocity stirs and progressively in polymers soln, slowly drip 2 times down to the precipitation agent deionized water of dioxane volume; Dropwise the back and continue at the uniform velocity to stir 3h, make micella stable in the deionized water with 6 times of dioxane volumes of the slow adding of mixing solutions then; Displace dioxane by dialysis method after continuing to stir 1h, control that the micella mass concentration is 0.6% in the final micellar aqueous solution, high voltage mercury lamp irradiation with 1kw solidifies 0.5h, and micellar surface generation illumination crosslinking reaction makes the micella immobilization, obtains the poly-weak electrolyte micelle wedding agent of both sexes.
(3) emulsion preparation
Get the poly-weak electrolyte micelle wedding agent of the prepared both sexes of step (2), transfer micellar solution 3mL and the isopyknic oily matter that is dissolved in the oil of a series of different pH, homogeneous under the speed of 5000rpm obtains the emulsion of a series of different emulsifying effectivenesses.The emulsifying effectiveness of this emulsion can be well controlled by the acid-basicity of system.
Simultaneously, gather the weak electrolyte micella because the main polymer of the micelle wedding agent of this emulsion is both sexes, therefore, this emulsion also has certain soda acid shock-absorbing capacity, can be used for special occasions.
Embodiment 6
(1) preparation of amphiphilic copolymer
By common free radical solution polymerization, poly-(vinylformic acid-2-(dimethylamino) ethyl ester-co-vinylformic acid) P (DM-co-AA) of synthetic full wetting ability polyelectrolyte.Weighing 4.29g (0.03mol) vinylformic acid-2-(dimethylamino) ethyl ester, 5.04g (0.07mol) vinylformic acid, 0.164g initiator Diisopropyl azodicarboxylate (0.001mol, press the monomer integral molar quantity 1.0%) in the 25mL ultrapure water, inflated with nitrogen 30 minutes, 70 ℃ are reacted 12h down, precipitate in the acetone of ultrapure water at 8 times, filter 30 ℃ of vacuum-dryings.Product is dissolved in the ultrapure water, and precipitation is filtered drying.Repeat above-mentioned steps three times, obtain purified amphiphilic copolymer.
(2) preparation of micelle wedding agent
Get the described polyelectrolyte of step (1) and in water, stir 12h, be dissolved into the polymers soln of mass concentration 0.5%, regulate the pH value of micellar solution, stir 6h by dripping small amount of hydrochloric acid or sodium hydroxide solution; By the adjusting of acid number, can control the micellar conformation of the micelle wedding agent solution of formation.
(3) emulsion preparation
Get described micelle wedding agent solution of 3mL step (2) and 3mL toluene, homogeneous 2min under 8000 rev/mins speed, the different emulsion emulsifying effectiveness that obtains is so can regulate and control the emulsifying capacity of the micelle wedding agent of this type of full wetting ability pH sensitivity by pH.
Embodiment 7
(1) preparation of amphiphilic copolymer
By free radical soap-free emulsion polymerization, amphiphilic copolymer gathers the synthetic of (vinylbenzene-co-vinylformic acid).In the mixed solvent of 15mL ethanol/water (volume ratio is 7: 3), add 0.75g vinylbenzene, 3.00g vinylformic acid, add 0.16g initiator Diisopropyl azodicarboxylate (monomer total amount 2.0mol%), reacted 8 hours, 40 ℃ of rotary evaporation etoh solvents and water, add 5mL methyl-sulphoxide dissolve polymer, in being the mixed solvent 50mL of 2/8 methanol, volume ratio precipitates suction filtration, 70 ℃ of oven dryings, circulate final required product three times.
(2) preparation of micelle wedding agent
Get poly-(vinylbenzene-co-vinylformic acid) and be dissolved in the solution that is made into mass concentration 5% in the tetrahydrofuran (THF).Under stirring condition, in polymers soln, dropwise slowly add 1.5 times of precipitation agent toluene, continue to stir 4 hours, then mixing solutions is slowly added 3.5 times of stirring and in the toluene of tetrahydrofuran (THF) volume, make micella stable to the tetrahydrofuran (THF) volume; Continue to stir 2 hours post-heating to 70 and ℃ steam tetrahydrofuran solvent, obtain the reversed phase micelle toluene solution, the micella mass concentration is 1.0% in the solution, can be used as the reversed phase micelle emulsifying agent and uses.
(3) emulsion preparation
Get reversed phase micelle emulsifying agent 3mL described in the step (2), 3mL water (perhaps other water-soluble substanceses) homogeneous 2min under the rotating speed of 10000rpm can obtain the special micelle wedding agent of water-in-oil-type, can be used for special occasions.
Embodiment 8
(1) preparation of amphiphilic copolymer
By free radical solution polymerization, synthetic poly-(N-N-isopropylacrylamide-co-vinylformic acid-co-(vinylformic acid-2-hydroxyethyl laurate)).Take by weighing 3.955g (35mmol) N-N-isopropylacrylamide, 0.72g (10mmol) vinylformic acid, 1.23g (5mmol) vinylformic acid-2-hydroxyethyl laurate, put into reaction flask, add the 20mL dioxane and make solvent, after the logical nitrogen 30min deoxygenation, add 0.164g initiator Diisopropyl azodicarboxylate (1mmol, the monomer integral molar quantity 2%), react 24h in 65 ℃ of oil baths.Reaction is made precipitation agent with deionized water after finishing, and reaction solution is added drop-wise in the big water gaging, and suction filtration obtains white solid, and then uses the tetrahydrofuran (THF) lysate, and with the deionized water precipitation, 3 times repeatedly, product vacuum-drying gets final product again.
(2) preparation of micelle wedding agent
It is 2% dimethyl formamide solution that multipolymer poly-(N-N-isopropylacrylamide-co-vinylformic acid-co-(vinylformic acid-2-hydroxyethyl laurate)) is made into starting point concentration.Constantly stir and in polymers soln, slowly drip 1 times down to the deionized water of dimethyl formamide volume; Dropwise the back and continue at the uniform velocity to stir 3h, make micella stable in the deionized water with 10 times of dimethyl formamide volumes of the slow adding of mixing solutions then; Dialysed 3 days in deionized water then, 12h changes water once, removes the dimethyl formamide that desolvates.The gained micellar aqueous solution can be used as micelle wedding agent.
(3) emulsion preparation
Get described micelle wedding agent of two parts of 3mL steps (2) and 3mL toluene, a copy of it is heated to 50 ℃ and carries out emulsification at 25 ℃ of following emulsifications, another part, the latter is because temperature surpasses the minimum critical phase transition temperature (LCST) of poly-(N-N-isopropylacrylamide-co-vinylformic acid-co-(vinylformic acid-2-hydroxyethyl laurate)), make the hydrophilic ability of micella greatly improve, can make it to lose emulsifying capacity and see Fig. 1, this emulsifying agent has temperature control susceptibility.
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (6)
1. the preparation method of an amphiphilic copolymer self-assembled micelle wedding agent is characterized in that technology is:
(1) preparation amphiphilic copolymer: amphiphilic copolymer is by hydrophilic monomer and hydrophobic monomer copolymerization, or several dissimilar hydrophilic monomer copolymerization or several dissimilar hydrophobic monomer copolymerization obtain;
Used hydrophilic monomer is selected from:
(a) maleic anhydride, (methyl) vinylformic acid, to vinyl benzoic acid;
(b) 4-vinylpridine, 2-vinyl pyridine, (methyl) vinylformic acid-2-(dimethylamino) ethyl ester, diethylamine ethyl-methyl acrylate;
(c) to vinylbenzenesulfonic acid, (methyl) acryloyl oxyethyl group trimethyl ammonium chloride, (methyl) acrylamide, N, N`-DMAA, N dimethylamine ethyl-methyl acrylamide;
(d) (methyl) vinylformic acid hydroxyl second (third) ester, N-N-isopropylacrylamide;
Used hydrophobic monomer is selected from:
(e) vinylbenzene, (methyl) esters of acrylic acid, vinyl acetate;
(f) (methyl) acryloyl ethoxy-cinnamic acid ester, 7-are to the inferior methoxy coumarin of vinyl benzene;
By the copolymerization process of two or more dissimilar monomer by common free radical solution polymerization, free radical dispersion polymerization, free-radical emulsion polymerization or free radical precipitation polymerization, the preparation amphiphilic copolymer;
(2) carry out the self-assembly of amphiphilic copolymer solution: in selective solvent, carry out the self-assembly of amphiphilic copolymer solution, obtain the amphiphilic copolymer micella; Selective solvent is made up of cosolvent and precipitation agent, wherein cosolvent can dissolve the polymer segment that two kinds of dissimilar monomers are formed simultaneously, selects for use: dimethyl formamide, dimethyl sulfoxide (DMSO), dioxane, tetrahydrofuran (THF), acetone, Virahol, butanols or mixed solvent; Precipitation agent is a kind of segmental good solvent in the multipolymer, is another kind of segmental precipitation agent in the multipolymer, selects for use: water, ethanol or toluene; Be dissolved in amphiphilic copolymer in the cosolvent fully, amphiphilic copolymer strength of solution scope is 0.5%-30%, stir the precipitation agent that slowly splashes into 0.1-2 times of cosolvent volume down, make multipolymer generation microphase-separated, self-assembly forms stable amphiphilic copolymer assembling micellar solution, dropwise the back at precipitation agent and continue at the uniform velocity to stir 2-12 hour, make the polymer chain assembling fully; The micella median size of being assembled out is between 10～800nm;
(3) micella immobilization: the amphiphilic copolymer of self-assembly assembling micellar solution is dropwise added 2-10 doubly in the precipitation agent of cosolvent volumetric usage, make micella stable; Continue to stir after 1-3 hour and displace cosolvent or adopt volatilization method to steam cosolvent by dialysis method, obtain amphipathic multipolymer assembling micellar solution, this amphipathic multipolymer assembling micella exists with micella particle solution form, or, use as micelle wedding agent through lyophilize or the spray-dried solid gums bundle of particle that obtains.
2. preparation method according to claim 1, what it is characterized in that being adopted is common free-radical polymerized, from the angle Selection of molecular designing dissimilar comonomer and ratio thereof, thereby regulates both sexes segmental ratio in the final resulting polymers segment; The adjusting of both sexes segment ratio in the polymkeric substance, the controllability of decision micelle wedding agent particle performance.
3. with the amphiphilic copolymer of claim 1,2 described method preparations, it is characterized by, make multipolymer have the responsive responsiveness of (a) pH by initial molecular designing; (b) temperature sensitive response; (c) ion-sensitive responsiveness; (d) photaesthesia responsiveness.
4. preparation method according to claim 1, it is characterized in that carrying out the self-assembly of amphiphilic copolymer solution, control final micella particle surface hydrophilic and hydrophobic, micella particle diameter by control selective solvent ratio, thereby control the emulsifying property of final micelle wedding agent.
5. with the micella particle of the described method preparation of claim 1, it is characterized in that the micella particle has the responsive responsiveness of (a) pH; (b) temperature sensitive response; (c) ion-sensitive responsiveness; (d) photaesthesia responsiveness.
6. use the application of the micella particle of the described method preparation of claim 1, it is characterized in that using as micelle wedding agent, emulsified oiliness composition is 1-1000 with the ratio of micella particle: 1 mixes; Oil or oiliness composition are selected for use: (1): toluene, hexanaphthene, octane, undecyl alcohol; (2): silicone oil, white oil, stearic acid; (3): heavy oil, kerosene, diesel oil; Or (4): oiliness dyestuff, oiliness initiator, oiliness solidifying agent.
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